EP0862937B1 - Temperaturwechseladsorption - Google Patents

Temperaturwechseladsorption Download PDF

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Publication number
EP0862937B1
EP0862937B1 EP98301574A EP98301574A EP0862937B1 EP 0862937 B1 EP0862937 B1 EP 0862937B1 EP 98301574 A EP98301574 A EP 98301574A EP 98301574 A EP98301574 A EP 98301574A EP 0862937 B1 EP0862937 B1 EP 0862937B1
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Prior art keywords
adsorbent
gas
alumina
temperature
carbon dioxide
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EP0862937A3 (de
EP0862937A2 (de
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Mohammed Ali Kalbassi
Timothy Christopher Golden
Rodney John Allam
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Air Products and Chemicals Inc
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Air Products and Chemicals Inc
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • B01D53/04—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
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    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
    • F25J3/02—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
    • F25J3/04—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream for air
    • F25J3/04151—Purification and (pre-)cooling of the feed air; recuperative heat-exchange with product streams
    • F25J3/04163—Hot end purification of the feed air
    • F25J3/04169—Hot end purification of the feed air by adsorption of the impurities
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • B01D53/04—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
    • B01D53/0407—Constructional details of adsorbing systems
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • B01D53/04—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
    • B01D53/0462—Temperature swing adsorption
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
    • F25J3/02—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
    • F25J3/04—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream for air
    • F25J3/04151—Purification and (pre-)cooling of the feed air; recuperative heat-exchange with product streams
    • F25J3/04157—Afterstage cooling and so-called "pre-cooling" of the feed air upstream the air purification unit and main heat exchange line
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
    • F25J3/02—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
    • F25J3/04—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream for air
    • F25J3/04151—Purification and (pre-)cooling of the feed air; recuperative heat-exchange with product streams
    • F25J3/04163—Hot end purification of the feed air
    • F25J3/04169—Hot end purification of the feed air by adsorption of the impurities
    • F25J3/04181—Regenerating the adsorbents
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
    • F25J3/02—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
    • F25J3/04—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream for air
    • F25J3/04763—Start-up or control of the process; Details of the apparatus used
    • F25J3/04769—Operation, control and regulation of the process; Instrumentation within the process
    • F25J3/04775—Air purification and pre-cooling
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/10—Inorganic adsorbents
    • B01D2253/104—Alumina
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/10—Inorganic adsorbents
    • B01D2253/106—Silica or silicates
    • B01D2253/108—Zeolites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/50—Carbon oxides
    • B01D2257/504—Carbon dioxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
    • B01D2257/702—Hydrocarbons
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/80—Water
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2259/00—Type of treatment
    • B01D2259/40—Further details for adsorption processes and devices
    • B01D2259/40011—Methods relating to the process cycle in pressure or temperature swing adsorption
    • B01D2259/40043—Purging
    • B01D2259/4005—Nature of purge gas
    • B01D2259/40052—Recycled product or process gas
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2259/00—Type of treatment
    • B01D2259/40—Further details for adsorption processes and devices
    • B01D2259/402—Further details for adsorption processes and devices using two beds
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2205/00—Processes or apparatus using other separation and/or other processing means
    • F25J2205/60—Processes or apparatus using other separation and/or other processing means using adsorption on solid adsorbents, e.g. by temperature-swing adsorption [TSA] at the hot or cold end
    • F25J2205/66—Regenerating the adsorption vessel, e.g. kind of reactivation gas
    • F25J2205/70—Heating the adsorption vessel
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2230/00—Processes or apparatus involving steps for increasing the pressure of gaseous process streams
    • F25J2230/04—Compressor cooling arrangement, e.g. inter- or after-stage cooling or condensate removal
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/40—Capture or disposal of greenhouse gases of CO2

Definitions

  • the present invention relates to temperature swing adsorption processes for removing at least carbon dioxide and water from a feed gas to form a purified gas for subsequent cryogenic treatment.
  • a feed gas When a feed gas is to be subjected to a cryogenic treatment such as for instance the cryogenic separation of air into oxygen and nitrogen, it is essential to remove components such as carbon dioxide and water which would freeze and interfere with the subsequent cryogenic treatment. It is also necessary to remove trace hydrocarbons such as acetylene if present which would otherwise accumulate in the cryogenic treatment and cause an explosion risk.
  • a cryogenic treatment such as for instance the cryogenic separation of air into oxygen and nitrogen
  • TSA temperature swing adsorption
  • PSA pressure swing adsorption
  • the flow of feed gas is shut off from the adsorbent bed and the adsorbent is exposed to a flow of purge gas which strips the adsorbed gas and water from the adsorbent and regenerates it for further use.
  • TSA the heat needed to desorb the carbon dioxide and the water from the adsorbent in the regeneration phase is supplied by heated regenerating gas.
  • PSA the pressure of the purge gas is lower than that of the feed gas and the change in pressure is used to remove the carbon dioxide and water from the adsorbent with the heat required for desorption being supplied by the heat of adsorption retained within the bed.
  • the pressure of the regenerating gas is lower than that of the feed gas in TSA also.
  • the adsorption phase is carried on for a prolonged period and the heat of adsorption of the carbon dioxide and water on the adsorbent liberated during most of the adsorption phase is displaced out of the bed by the flow of gas. It is necessary that the adsorbent bed has a substantial capacity for adsorbing carbon dioxide and water.
  • the duration of the adsorption phase has to be short so that the heat of adsorption is not displaced out of the bed by the flow of feed gas before the regeneration phase starts. Because of the short cycle used, it is not necessary that the adsorbent has any substantial capacity for the components which are being adsorbed.
  • a bed of alumina upstream of the zeolite adsorbent serves to adsorb most of the water, leaving the zeolite to adsorb the carbon dioxide.
  • alumina and molecular sieve zeolite in this way is further described in US-A-4711645 (Kumar) in the context of PSA.
  • the benefit of using an upstream bed of alumina in the adsorbent is that because the heat of adsorption of water in alumina is less than that in zeolite, there is a lower overall temperature change in the initial water removal step than if one employed a single bed of zeolite for removal of water and carbon dioxide.
  • a more effective operation is provided by the process because of the adsorption capacity of the zeolite at the lower adsorption temperature of the bed which is then obtainable.
  • US-A-5232474 proposes the use of an alumina adsorption bed for the removal of both water and carbon dioxide from air prior to cryogenic air separation.
  • the process used is PSA and is operated so as to remove at least 90 percent of the carbon dioxide from the gas stream.
  • a second adsorption zone is provided containing a zeolite to remove residual carbon dioxide and other impurities such as hydrocarbons from the gas stream. It is noted there that the use of alumina to remove substantial amounts of carbon dioxide was contrary to the teachings of the art which recognised its use only for removing moisture from gas streams.
  • Activated alumina has, at most, only one fifth of the absolute capacity of 13X zeolite for carbon dioxide adsorption.
  • alumina has the ability to be completely regenerated in PSA processes whereas 13X zeolite is only partially regenerated and that under PSA conditions, the effective carbon dioxide capacity (the difference between adsorption and regeneration step loadings) for activated alumina was therefore at least as high as 13X zeolite with the added advantage that the alumina adsorbs significantly less nitrogen rich waste gas compared to zeolite so reducing vent gas loses by 50 percent or more with considerable energy savings.
  • US-A-4249915 discloses the use of alumina in a PSA section of an adsorbent apparatus which also has a TSA section containing zeolite.
  • the PSA section containing alumina is used for removing water and the TSA section is used for removing carbon dioxide. It is indicated that the TSA section must employ an adsorbent selective towards very dilute CO 2 such as certain molecular sieves, clearly implying that the alumina used in the PSA section cannot be used in TSA.
  • US-A-3865924 (Gidaspow) describes the removal of carbon dioxide from a gas stream using a modified alumina.
  • the process is described as being particularly suitable for removal of carbon dioxide from air being breathed in confined quarters such as submarines although it is indicated that the process may be used for the removal of carbon dioxide from various gases such as the removal of carbon dioxide from hydrogen for feeding a fuel cell.
  • the process described is essentially a TSA process.
  • the alumina adsorbent is in powdered form and is modified by being mixed with finely divided alkali metal carbonate, especially potassium carbonate.
  • the presence of water is essential to the sorption of the carbon dioxide by this composition, the carbon dioxide undergoing a chemical reaction with the potassium carbonate and the water to form bicarbonate. It is indicated that the adsorbent can be regenerated at temperatures of 80°C or above and that the differential in temperature between the adsorption and the regeneration stages can be as little as 20°C.
  • the process described is however unsuitable for large-scale operation and is unsuitable for use prior to a cryogenic process.
  • the presence of water is indicated to be essential to the sorption process described. Accordingly, the output gas is not to be dried and could not therefore be supplied as the feed gas of a cryogenic process.
  • the adsorbent is powdered and could not be used in a large-scale adsorption process because of the enormous pressure drop which a powdered adsorbent would create.
  • US-A-3557025 (Emerson) describes the use of alumina mixed with alkali metal bicarbonate and heated to a temperature of 150°C for a period of hours to produce a compound of the formula NaAl(OH) 2 CO 3 . This is used for the adsorption of sulphur dioxide but it is not disclosed that the adsorbent is capable of being regenerated.
  • US-A-3629153 (Pryer) describes the preparation of an alkalised alumina composition by adding granular or hydrated alumina to hot sodium hydroxide solution and reacting the product with ammonium carbonate or carbon dioxide.
  • the product of this reaction (dawsonite) is converted to alkalised alumina by heating at temperatures of up to 1000°C.
  • the product is useful for the adsorption of water vapour, hydrogen sulphide, sulphur dioxide and other acidic type gases. It is not suggested that the product could be useful in a TSA process for adsorbing carbon dioxide and water.
  • US-A-4433981 does relate to removing carbon dioxide from gas streams, typically hydrocarbon process streams or breathable air. It discloses impregnating a porous aluminum oxide support with an alkali metal compound decomposable on calcination to the alkali metal oxide and heating at calcination temperatures. Regeneration of the adsorbent is conducted at very high temperatures such as 575°C for prolonged periods such as 16 hours. Such an adsorbent would not be economically useful in a TSA process for purifying a gas prior to a cryogenic operation, having regard to the extremely high energy requirement for the regeneration step.
  • activated alumina can be used in a TSA system which can operate at a low regeneration temperature if desired, with the alumina serving to adsorb the water from the feed gas and all or most of the carbon dioxide.
  • Other undesirable components if present may also be wholly or partially adsorbed and removed, such as hydrocarbons including acetylene and nitrogen oxides.
  • the present invention now provides a process for the temperature swing adsorption of at least carbon dioxide and water from a feed gas to form a purified gas for subsequent cryogenic treatment, comprising contacting the feed gas at a first temperature with a solid adsorbent comprising agglomerates of activated alumina, so as to produce a dry, purified gas from which at least most of the carbon dioxide has been removed, and periodically regenerating the adsorbent by contacting the adsorbent with a regenerating gas at a second temperature in excess of said first temperature characterised in that said activated alumina is impregnated with a basic solution having a pH of 9 or more and dried at a temperature which is not so high as to produce decomposition of the impregnant to produce oxide and said second temperature is not so high as to produce decomposition of the impregnant to produce oxide.
  • references herein to the water and carbon dioxide being removed we mean the reduction of the water and carbon dioxide content to the level required for the supply of the gas for use in a cryogenic process.
  • the feed gas is preferably air and the process according to the invention may further comprise subsequent cryogenic treatment of the purified air produced by the adsorption process defined above.
  • the cryogenic process may preferably be a cryogenic air separation process, e.g., one in which oxygen is separated from nitrogen.
  • gases may be treated to remove carbon dioxide and water in accordance with the invention including natural gas, hydrocarbons and synthesis gas containing low levels of CO 2 .
  • the alumina is present in the process in the form of agglomerates such as granules or beads.
  • agglomerates such as granules or beads.
  • the production of activated alumina in the form of such agglomerates is well known in the art and requires no detailed description here.
  • alumina is mixed with water and is heated to form nonfriable robust agglomerates which can be packed into an adsorbent bed to produce low pressure drop and resistance to the production of fine particles (dust).
  • activated alumina includes such materials as are commercially available. Those skilled in the art are aware that such materials typically are not 100 percent alumina and will contain small percentages of other materials such as ferric oxide, sodium oxide, silica and the like. Certain commercially available activated alumina products are even formulated to contain specified amount of these and other materials to enhance their activity and confer other beneficial properties.
  • Activated aluminas for use in this invention may be conventional alumina (e.g., Alcan AA300, Alcan F200, La Roche A201, Rhone Poulenc Grade A etc.) with typical physical and chemical properties as shown below: Chemical Analysis Wt% SiO 2 0.02 Fe 2 O 3 0.02-0.04 TiO 2 0.002-0.01 Na 2 O 0.3-0.4 Al 2 O 3 >93 Loss on Ignition 3-7 All of the above products can be used in the process of this invention.
  • conventional alumina e.g., Alcan AA300, Alcan F200, La Roche A201, Rhone Poulenc Grade A etc.
  • Chemical Analysis Wt% SiO 2 0.02 Fe 2 O 3 0.02-0.04 TiO 2 0.002-0.01 Na 2 O 0.3-0.4 Al 2 O 3 >93 Loss on Ignition 3-7 All of the above products can be used in the process of this invention.
  • the purification process is conducted in such a way that the purified gas produced is dry, i.e., water-free to the extent of having a dew point compatible with cyrogenic applications, e.g., of -180°C or less.
  • the adsorption process is operated to remove at least about 70 percent, more preferably 80 percent and most preferably at least 85 or 90 percent of the carbon dioxide contained in the gas stream.
  • the process is conducted so as to adsorb substantially all the carbon dioxide contained in the gas stream within the alumina bed.
  • further means may be provided for removing the remainder of the carbon dioxide from the gas stream after the alumina adsorption process.
  • a body of zeolite downstream (in the direction of feed gas flow) from the alumina adsorbent for adsorbing residual carbon dioxide and/or hydrocarbons there is preferably provided a body of zeolite downstream (in the direction of feed gas flow) from the alumina adsorbent for adsorbing residual carbon dioxide and/or hydrocarbons.
  • the zeolite may be of various kinds, 13X zeolite is particularly preferred.
  • the zeolite may be present in a second adsorption bed but more preferably forms a downstream part of a composite adsorption bed containing also the alumina. The process may be operated such that the alumina serves normally to adsorb all of the carbon dioxide with the zeolite being present to act as a guard against the breakthrough of carbon dioxide and hydrocarbons if present.
  • the zeolite in the second adsorption bed may be mixed with alumina.
  • the water content of the feed gas may be reduced prior to the TSA adsorption process by cooling the feed gas to condense water from it in a manner known in the art
  • the pH of the impregnating solution is at least 10, more preferably from 10 to 12. Best results have been obtained using an impregnating solution having a pH of about 11.
  • the pH of the impregnating solution is related to the zero point charge (zpc) of the alumina according to the formula: pH ⁇ zpc-1.4 or more preferably by the formula: zpc + 2 ⁇ pH ⁇ zpc - 1.4
  • the pH of the impregnating solution is related to the zero point charge of the alumina by the formula: zpc + 1 ⁇ pH ⁇ zpc - 1
  • Said basic solution may suitably be a solution of an alkali metal or ammonium compound such as one selected from hydroxides, carbonates, bicarbonates, phosphates, and organic acid salts.
  • Suitable basic compounds that may be employed include sodium, potassium or ammonium carbonate, hydroxide, phosphate bicarbonate, nitrate, formate, acetate, benzoate or citrate.
  • the most suitable basic compound for use in the invention is potassium carbonate.
  • the TSA process of the invention may be applied to the removal of water and carbon dioxide from gas streams in which carbon dioxide is present at a low level such as 400 ppm carbon dioxide prior to the adsorption process.
  • TSA TSA, one normally employs a flow of a regenerating gas, low in CO 2 content, normally nitrogen rich wash gas from a downstream air separation unit to desorb the CO 2 from the adsorbent.
  • the feed gas is supplied at a pressure of from 2 to 20 bara, more preferably 2 to 15 bara.
  • Feed gas is preferably supplied at a temperature of from 5 to 50°C, more preferably from 10 to 40°C.
  • the process is operated at a P/A ratio (molar flow of regenerating gas to feed gas) of from 0.1 to 0.8, more preferably from 0.2 to 0.5.
  • P/A ratio molecular flow of regenerating gas to feed gas
  • the gas is fed to the adsorbent for a period of from 60 to 600 minutes prior to regeneration of the adsorbent.
  • the most advantageous time period here will depend upon the size of the adsorbent bed used. Generally, it will be preferable for the on-line period to be from 70 to 300 minutes.
  • the regenerating gas should be fed to the adsorbent at a temperature which exceeds the temperature of the feed gas.
  • the regenerating gas is preferably fed at a temperature of from 30 to 150°C. Suitably it is fed at a pressure of 0.5 to 8 bara and
  • the regenerating gas is fed to the adsorbent at a pressure of from 1 to 3 bara. Note however that the system could be designed with regenerating gas pressure higher than the feed gas pressure provided the purge to feed ratio and the purge temperature were high enough.
  • zeolite downstream of the alumina for adsorbing residual carbon dioxide or hydrocarbons and suitably this makes up 5 to 30% v/v of the total adsorbent.
  • adsorbent As is conventional in a TSA operation, there are preferably at least two separate bodies or beds of adsorbent which can be placed on-line in substitution for one another whilst regeneration is taking place in another or the other bed.
  • the apparatus used for conducting the process according to the invention may be conventional TSA apparatus as previously widely described and used in this art except of course for the substitution of the alumina adsorbent required in the present invention for the zeolite or alumina/zeolite adsorbents previously employed.
  • apparatus for use in practising the invention comprises at least a pair of adsorbent beds containing columns or vessels 2, 4 each containing an alumina adsorbent as described in detail hereafter.
  • Air to be purified is supplied to the apparatus from a main air compressor 6. Heat produced during the compression of the air in the compressor 6 is removed as described later if desired in heat exchangers 8 and 10.
  • the compressed air is then supplied to inlet manifold 12 containing control valves 14 and 16 to which is connected the pair of adsorbent bed containing columns 2 and 4.
  • the inlet manifold is bridged downstream of the control valves 14, 16 by a venting and depressurising manifold 18 containing venting valves 20 and 22 which serve to dose and open connections between the upstream ends of respective adsorbent columns 2 and 4 and a vent 30 fitted with a silencer 32.
  • the apparatus has an outlet for purified gas 34 connected to the downstream ends of the two adsorbent columns 2, 4 by an outlet manifold 36 containing control valves 38 and 40 upstream of which the outlet manifold 36 is bridged by a regenerating gas manifold 42 connected to a line 44 supplying regenerating gas as described in more detail hereafter and containing control valves 46, 48 by which the flow of regenerating gas may be connected selectively to either of the adsorbent containing columns 2, 4.
  • a further manifold 50 containing a control valve 52 bridges between the downstream ends of the columns 2, 4 for the purpose of repressurisation.
  • the purified gas produced is supplied to the cold box of an air separation unit which separates air into oxygen and nitrogen. Dry carbon dioxide-free gas from the cold box is supplied to the illustrated apparatus at an inlet 56 which is connected to the inlet for regenerating gas 44 via two selectable paths 58 and 60 controlled by respective control valves 62 and 64. Path 58 leads the regenerating gas directly to the regenerating gas inlet 44 whereas path 60 leads through a heat exchanger 66 in which the regenerating gas receives heat from water circulated by a pump 68 through heat exchanger 8 and heat exchanger 66.
  • Heat exchanger 10 is provided with a cold water inlet and a cold water outlet for controlling the temperature of the feed gas supplied to the apparatus.
  • control valves may be controlled by suitable programmable timing and valve operating means as known in the art.
  • air is compressed in the main air compressor 6 and is supplied to the inlet manifold 12 from where it is fed into one of the two adsorbent columns or vessels 2, 4, depending upon which is currently on-line and which is in its regeneration phase.
  • Purified air leaving the column passes via open valve 38 or open valve 40 to the outlet 34 and hence to the cold box of the air separation process. If it is column 2 which currently on-line, then valves 16, 20, 52, 46 and 40 would all be closed at this stage. The flow of gas through the column 2 is continued until the adsorbent is so loaded with water and carbon dioxide that it is necessary for it to be regenerated.
  • valves 14 and 38 are closed and valves 16 and 40 are opened to place the other column 4 on-line and to allow column 2 to be regenerated.
  • valve 20 is opened to depressurise the column through vent 30. Dry nitrogen rich waste gas from the cold box is then introduced through valve 64 to pass through the heat exchanger 66 where it is warmed to a regeneration temperature and supplied through inlet 44 to the downstream end of the column 2 through which the gas passes in the reverse of the feed direction to the vent 30.
  • valve 64 When sufficient heat has been supplied for regeneration, valve 64 is closed and valve 62 is opened so as to supply cool regenerating dry nitrogen rich waste gas and to lower the temperature of the bed before it goes back on-line so as to avoid sending heat to the cold box following repressurisation.
  • the operation is reversed so that valves 14 and 38 are reopened and column 2 is placed back on-line while column 4 is regenerated.
  • a further option is direct compression of the purge stream to a desired pressure whereby the heat of compression is utilised to provide the desorption energy for the TSA system.
  • This is illustrated in Figure 2 in which the arrangement is identical to that shown in Figure 1 except that heat exchangers 8, 10 and 66 are omitted.
  • the purge gas is instead heated as a result of being compressed in a compressor 70, with cooling when appropriate in a cooler 72 controlled by valves 62, 64.
  • FIG. 3 An alternative arrangement is shown in Figure 3 in which the compressor 70 is omitted and the purge gas is heated in a heater 74 when required and supplied via a bypass controlled by valves 62, 64 when heating is not required.
  • a subcooler may be provided between the main air compressor 6 and the inlet manifold 12.
  • the adsorbent may be activated alumina of a conventional kind or it may be a modified activated alumina which has been impregnated with a basic material to improve its capacity.
  • a modified alumina for use in the invention may be prepared by making a solution of the chosen basic compound having an appropriate pH as described above and adding the solution to an alumina in a volume just sufficient to fill the pores of the alumina without producing surface wetness.
  • the concentration and the amount of the solution may be chosen to produce a loading of the compound on the alumina of from 1 to 15 percent on a dry weight basis, e.g., 1 to 10 percent.
  • the treated alumina should be dried at a temperature which is not so high as to produce decomposition of the added compound to produce oxide which will bind carbon dioxide in a manner which cannot be reversed by reducing the gas pressure and heating to a low temperature, e.g., by 50°C, but only by elevated temperature.
  • a low temperature e.g., by 50°C, but only by elevated temperature.
  • US-A-4433981 discloses treating alumina with a solution of sodium carbonate or other compounds, drying at 100°C, and then heat treating further at 575°C. This second heating step produces a material which is unsuitable for use in the processes of this invention.
  • Drying is therefore preferably carried out at below 200°C, more preferably below 150°C.
  • the compound used to impregnate the alumina for use in the present invention should not cause water to react with the adsorbent so that it is not desorbed under the temperature swing conditions used. Nonreversible adsorption of water will progressively interfere with the adsorption of carbon dioxide.
  • zero point charges of aluminas are measured by placing 20 grams of alumina in water and testing the pH after 24 hours.
  • Henry's law constants (K 2 ) were measured as initial isotherm slopes in units of mmole/gram/bar after outgassing at a pressure of 50 ⁇ m (microns) of Hg (6.7 Pa) for 16 hours at 25°C, followed by repeated dosing with CO 2 at 30°C and subsequent evacuation at 50 microns Hg (6.7 Pa) pressure for 16 hours.
  • Initial Henry's law constants (K 1 ) were measured similarly during the first dosing with CO 2 .
  • High K 1 values represent a larger capacity for adsorbing carbon dioxide in a manner that is reversible only by high temperature treatment.
  • High K 2 values indicate the high regenerable (by pressure swing or by TSA at low temperatures) capacities desired for the present invention.
  • Adsorbent pH of impregnating solution (mmole/g/bar) K 1 (mmole/g/bar) K 2 Alcan AA-300 - 14.8 5.6 5% Fe(NO 3 ) 3 1.2 1.3 1.2 5% Citric Acid 1.7 0.92 0.88 5% Csl 5.8 2.0 1.6 5% NH 4 HCO 3 7.8 6.3 4.9 5% (NH 4 ) 2 CO 3 8.9 6.6 5.8 5% K 2 CO 3 11.4 81.0 22.8 5% Na 3 PO 4 12.7 12.4 12.2 5% NaOH 13.1 340 15.1
  • Table 1 clearly show that impregnation of alumina with acidic solutions reduces the CO 2 capacity of the material.
  • basic solutions above a pH of 9 significantly increase the K 2 value for CO 2 indicating that making the surface of alumina more basic enhances CO 2 capacity.
  • Air purification to remove H 2 O and CO 2 and trace hydrocarbons was performed using a bed of AA300 (1.2-2.4 mm) activated alumina impregnated with 5% w/w K 2 CO 3 .
  • the purge step is in two parts. In the first step the system is purged by preheating the purge stream at 80°C. In the latter part the system is regenerated at 28°C by which the adsorbent bed is also cooled down.
  • Feed Conditions 400 ppm CO 2 , Full Water Saturation, 1 ppm C 2 H 2

Claims (26)

  1. Verfahren für die Temperaturwechseladsorption von mindestens Kohlendioxid und Wasser aus einem Einspeisgas zur Bildung eines gereinigten Gases für die folgende kryogenische Behandlung, umfassend das In-Kontakt-bringen des Einspeisgases bei einer ersten Temperatur mit einem festen Adsorptionsmittel, umfassend Agglomerate von aktiviertem Aluminiumoxid, um ein trockenes, gereinigtes Gas zu erzeugen, aus dem mindestens das meiste des Kohlendioxids entfernt worden ist, und periodisches Regenerieren des Adsorptionsmittels durch In-Kontakt-bringen des Adsorptionsmittels mit einem regenerierenden Gas bei einer zweiten Temperatur oberhalb der ersten Temperatur, dadurch gekennzeichnet, dass dasaktivierte Aluminiumoxid mit einer basischen Lösung mit einem pH-Wert von 9 oder darüber imprägniert und bei einer Temperatur getrocknet wird, die nicht so hoch ist, dass sie die Zersetzung des Imprägniermittels zur Erzeugung von Oxid bewirkt, und wobei die zweite Temperatur nicht so hoch ist, dass sie die Zersetzung des Imprägniermittels zur Erzeugung von Oxid bewirkt.
  2. Verfahren gemäß Anspruch 1, worin das Einspeisgas Luft, Erdgas oder Synthesegas ist.
  3. Verfahren gemäß Anspruch 2, zusätzlich umfassend die folgende kryogenische Trennung der Luft.
  4. Verfahren, wie in einem der Ansprüche 1 und 3 beansprucht, worin der pH-Wert der imprägnierenden Lösung mindestens 10 ist.
  5. Verfahren gemäß Anspruch 4, worin der pH-Wert der imprägnierenden Lösungen von 10 bis 12 beträgt.
  6. Verfahren gemäß Anspruch 4, worin der pH-Wert der imprägnierenden Lösung etwa 11 beträgt.
  7. Verfahren gemäß Anspruch 4, worin der pH-Wert der imprägnierenden Lösung mit der Nullpunktsladung (= zero point charge) des Aluminiumoxids gemäß der folgenden Formel in Beziehung steht: pH ≥ zpc - 1,4
  8. Verfahren gemäß Anspruch 7, worin der pH-Wert der imprägnierenden Lösung mit der Nullpunktsladung des Aluminiumoxids über die folgende Formel in Beziehung steht: zpc+2 ≥ pH ≥ zpc- 1,4
  9. Verfahren gemäß Anspruch 8, worin der pH-Wert der imprägnierenden Lösung mit der Nullpunktsladung des Aluminiumoxids über die folgende Formel in Beziehung steht: zpc + 1 ≥ pH ≥ zpc - 1
  10. Verfahren, wie in einem der vorstehenden Ansprüche beansprucht, worin die basische Lösung eine Lösung einer Alkali- oder Ammoniumverbindung darstellt.
  11. Verfahren, wie in einem der vorstehenden Ansprüche beansprucht, worin die Verbindung ausgewählt ist aus der Gruppe, bestehend aus Hydroxiden, Carbonaten, Bicarbonaten, Phosphaten und organischen Salzen.
  12. Verfahren, wie in einem der vorstehenden Ansprüche beansprucht, worin das Einspeisgas bei einem Druck von 2 bis 20 bara zugeführt wird.
  13. Verfahren, wie in einem der vorstehenden Ansprüche beansprucht, worin das Einspeisgas bei einem Druck von 2 bis 15 bara zugeführt wird.
  14. Verfahren, wie in einem der vorstehenden Ansprüche beansprucht, worin das Einspeisgas bei einer Temperatur von 5 bis 50° C bereitgestellt wird.
  15. Verfahren gemäß Anspruch 14, worin das Einspeisgas bei einer Temperatur von 10 bis 40° C bereitgestellt wird.
  16. Verfahren gemäß einem der vorstehenden Ansprüche, das bei einem P/A-Verhältnis von 0,1 bis 0,8 betrieben wird.
  17. Verfahren gemäß Anspruch 16, das mit einem P/A-Verhältnis von 0,2 bis 0,5 betrieben wird.
  18. Verfahren, wie in einem der vorstehenden Ansprüche beansprucht, worin Gas in das Adsorptionsmittel für eine Zeitspanne von 60 bis 600 Minuten eingespeist wird, vor Regeneration des Adsorptionsmittels.
  19. Verfahren, wie in Anspruch 18 beansprucht, worin das Gas dem Adsorptionsmittel für eine Zeitspanne von 70 bis 300 Minuten zugeführt wird, vor der Regeneration des Adsorptionsmittels.
  20. Verfahren, wie in einem der vorstehenden Ansprüche beansprucht, worin das Gas zum Regenerieren des Adsorptionsmittels bei einer Temperatur von 30 bis 150° C eingespeist wird, was die Temperatur des zum Adsorptionsmittels zugeführfen Einspeisgases um von 25 bis 110° C übersteigt.
  21. Verfahren, wie in einem der vorstehenden Ansprüche beansprucht, worin das Regenerationsgas dem Adsorptionsmittel bei einem Druck von 0,5 bis 8 bara zugeführt wird.
  22. Verfahren, wie in Anspruch 21 beansprucht, worin das Regenerationsgas dem Adsorptionsmittel bei einem Druck von 1 bis 3 bara zügeführt wird.
  23. Verfahren, wie in einem der vorstehenden Ansprüche beansprucht, worin das Adsorptionsmittel zusätzlich einen Körper aus Zeolit stromab (in Richtung des Einspeisgasstromes) von dem Aluminiumoxid als Adsorptionsmittel zum Adsorbieren von rückständigem Kohlendioxid und/oder Kohlenwasserstoffen umfasst.
  24. Verfahren, wie in Anspruch 23 beansprucht, worin der Zeolit als Adsorptionsmittel von 5 bis 30 % (Volumen/Volumen) des Gesamtadsorptionsmittels ausmacht.
  25. Verfahren, wie in Anspruch 23 beansprucht, worin mindestens 70 % des Kohlendioxids in dem Aluminiumoxid als Adsorptionsmittel adsorbiert werden.
  26. Verfahren, wie in Anspruch 23 beansprucht, worin mindestens 80 % des Kohlendioxids in dem Aluminiumoxid als Adsorptionsmittel adsorbiert werden.
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DE69815171D1 (de) 2003-07-10
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KR19980079968A (ko) 1998-11-25
DE69815171T2 (de) 2003-12-11
US5846295A (en) 1998-12-08
CA2230746A1 (en) 1998-09-07
TW354264B (en) 1999-03-11
CA2230746C (en) 2002-01-01
ES2195274T3 (es) 2003-12-01
CN1113680C (zh) 2003-07-09
CN1198358A (zh) 1998-11-11
JPH11518A (ja) 1999-01-06
JP2988625B2 (ja) 1999-12-13
KR100271539B1 (ko) 2000-11-15

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